Funzionalizzazione di allotropi del carbonio sp2 a partire da building block C-3 e C-6

Functionalization of sp

2

carbon allotropes

from Bio-sourced C3 and C6 Building Blocks

Politecnico di Milano, Department of Chemistry, Materials and Chemical Engineering “G. Natta”

Vincenzina Barbera,

Politecnico di Milano, Department of Chemistry, Materials and Chemical Engineering “G. Natta”

ISCaMaP

I

nnovative

S

ustainable

C

hemistry and

M

aterials and

P

roteomics

Group

 Strategy of Research

 C-3 and C-6 building blocks

 Valorization:

functionalization of carbon allotropes

ISCaMaP

 Chemicals, Additives, Modifiers, Polymers

Natural sources

Innovative

chemicals

Innovative

materials

Wastes and residues

_{Circular materials}

Building blocks

for chemical platforms

Glycerol, Sugars

The ISCaMaP Group. Some examples

OH

HO

OH

OH

HO

NH

₂

…

…

OH

HO

OH

OH

HO

OH

From glycerol to serinol

OH

HO

 Starting building block for many reaction pathways: many derivatives

 Chemoselectivity

OH

HO

NH

₂

Reactions of the amino group with carbonyl compounds

Selection of the building block: serinol

Reaction of serinol with dicarbonyl compound

V. Barbera, A.Citterio, M. Galimberti, G. Leonardi, R. Sebastiano, S.U.Shisodia, A.M. Valerio WO 2015 189411 A1

M. Galimberti, V. Barbera, A. Citterio, R. Sebastiano, A. Truscello, A. M. Valerio, L. Conzatti, R. Mendichi, Polymer, vol 63, 20 April 2015, Pages 62–70 M. Galimberti, V. Barbera, S. Guerra, L. Conzatti, C. Castiglioni, L. Brambilla, A. Serafini,, RSC Adv., 2015, 5, 81142-81152 DOI: 10.1039/C5RA11387C

V. Barbera, S. Musto, A. Citterio, L. Conzatti, M. Galimberti,, eXPRESS Polymer Letters 2016, 10 (7) 548–558

Serinol pyrrole - SP

2-(2,5-dimethyl-1H-pirrol-1-yl) -1,3-propanediol

180°C, 3 h

RT, 8 h

Neat synthesis of Serinol pyrrole

From sp

3

to sp

2

Paal-Knorr reaction

 Yield: at least

96%

 Atom efficiency:

85%

 Easy procedure



No solvent

 By product:

H

₂

O

Pyrrole compounds (PyC) from neat Paal Knorr reaction

O

O

+

_H

N

R

N

R

∆

+

2

H

₂

O

H

₂

N

OH

O

Si

O

O

O

NH

Yield %

75

62

73

80

70

PyC

V. Barbera, A. Bernardi, A.Palazzolo, A. Rosengart, L. Brambilla, M. Galimberti Pure and Applied Chemistry 2018, 90(2), 253–270

80

IUPAC: (2R,3S,4R,5S)-2,3,4,5-tetrahydroxyhexanedioic acid

Common nomenclature:

mucic acid

Formula: C

₆

H

₁₀

O

₈

210.14 Da

 Symmetrical structure: achiral

 Platform molecule

 Not toxic, Biocompatible

 25 times less expensive than glucaric acid

Chemicals from sugars. Galactaric Acid

H

OH

HO

H

HO

H

OH

H

O

HO

HO

O

Production (ton/a) 100,000 (6-40 $/kg)*

Production (ton/a) 38,000 (4-10 $/kg)*

IUPAC: (2R,3S,4R,5S)-2,3,4,5-tetrahydroxyhexanedioic acid

Common nomenclature: mucic acid

Formula: C

₆

H

₁₀

O

₈

210.14 Da

Galactaric Acid

H

OH

HO

H

HO

H

OH

H

O

HO

HO

O

pretty high price

However …

IUPAC: (2R,3S,4R,5S)-2,3,4,5-tetrahydroxyhexanedioic acid

Common nomenclature: mucic acid

Formula: C

₆

H

₁₀

O

₈

210.14 Da

Galactaric Acid

H

OH

HO

H

HO

H

OH

H

O

HO

HO

O

Improvements in the production techniques would

unlock its potential as a platform chemical

low price

☺

pretty high price

Galactaric Acid - Platform molecule

Derivatives from galactaric acid

O

OX

OH

HO

OY

HO

YO

O

-COOH

-

OH

Dehydration

f or

lactone

f ormation

Role

of

aldarate

salts

_(both

inorganic

and

organic)

Acylation

of

hydroxy

groups

Amidation

f or

amide

salts,

diamides

and

polyamides

O

Esterif ication

Mono

Elimination

Dielimination

into

value-added produ

Hydrogenation

f or

reduced

products

Galactaric Acid - Platform molecule

-COOH

-

OH

Dehydration

f or

lactone

f ormation

Role

of

aldarate

salts

_(both

inorganic

and

organic)

Acylation

of

hydroxy

groups

O O

Amidation

f or

amide

salts,

diamides

and

polyamides

O

Esterif ication

Mono

Elimination

Dielimination

into

value-added products

pyrones

f urans

pyrroles

Hydrogenation

f or

reduced

products

H2

Derivatives from galactaric acid

J. LI –PhD thesis 2019 – Politecnico di Milano

Synthesis of Pyrone Derivatives from Galactaric Acid

 Easy procedure

 High Conversion

 High Atom efficiency

Synthesis of Pyrrole Derivatives from 2-Hydroxypyrones

J. LI –PhD thesis 2019 – Politecnico di Milano

O

O

OH

X

+

2

R

NH

X

_N

O

H

N

R

R

R

R

2

- 2H

₂

O

neat

∆

1; X = COO

-Na

+

2; X = COOH

3; X = H

PR

₁

_{; X = COO}

-

Na

+

PR

₂

_{; X = COOH}

PR

₃

_{; X = H}

Synthesis of Pyrrole Derivatives from 2-Hydroxypyrones

Subs.

Amine (equiv.)

T

(°C)

t

(h)

Conv. %

PR1

(Yield %)

PR2

(Yield %)

PR3

(Yield %)

1

Ethanolamine (5)

50

24

45

35

-

6

1

Ethanolamine (10)

50

63

98

94

-

0.6

1

Octylamine (10)

50

43

79

76

-

3

2

Ethanolamine (6.0)

50

24

100

-

95

0.6

2

Isoserinol (5.9)

50

26

98

-

95

0

2

Serinol (5.9)

70

21

97

-

93

6

2

Benzylamine (5.4)

75

20

92

-

71

21

2

Octylamine (10)

65

23

100

-

87

7

3

Ethanolamine (6)

50

24

100

-

-

75

3

Octylamine (10)

65

24

100

-

-

80

J. LI –PhD thesis 2019 – Politecnico di Milano

O

O

OH

X

+

2

R

NH

X

_N

O

H

N

R

R

R

R

2

- 2H

₂

O

neat

∆

1; X = COO

-Na

+

2; X = COOH

3; X = H

PR

₁

_{; X = COO}

-

Na

+

PR

₂

_{; X = COOH}

PR

₃

_{; X = H}

Serinolpyrrole: Janus molecule

N

OH

HO

INTERACTION

WITH

LIPOPHILIC MATRIX

AND

GRAPHITIC CARBONS

REACTIONS WITH

FUNCTIONAL GROUPS

INTERACTION

WITH POLAR

SURROUNDING

Objective of the research

Sustainable and versatile functionalization

of unperturbed graphene layers

graphene

stacked graphene layers

CNT

stacked

randomly

arranged

wrapped

with different

shape anisotropy

carbon black

graphite,

nano-graphite,

graphene

CNT

CB

FEW LAYERS

GRAPHENE

Adducts of SP with CA - Preparation

Carbon

allotrope

CA-SP

CA/

SP

Ball Milling

(300 rpm 6h)

CA/SP-M

adduct

CA/SP-T

adduct

Thermal

treatment

80 – 180°C

Mechanical treatment

Thermal treatment

Barbera, V., Citterio, A., Galimberti, M., Leonardi, G., Sebastiano, R., Shisodia, S.U., Valerio A.M. WO 2015 189411 A1

Galimberti, M., Barbera, V., Sebastiano, R., Citterio, A., Leonardi, G. WO/2016/050887 A1 (2016)

High yield functionalization!

BET Surface area:

300 77 275

[m

_/g]

Initial functional groups:

1.7 0.9 2.0

[mmol/g]

Yields (%)*:

96 82 92

Adducts of SP with HSAG

M. Galimberti, V. Barbera, S. Guerra, L. Conzatti, C. Castiglioni, L. Brambilla, A. Serafini, RSC Adv., 2015, 5, 81142-81152 M. Galimberti, V. Barbera, R. Sebastiano, A. Citterio, G. Leonardi, A.M. Valerio WO 2016 050887 A1



Functional groups up to 20%



In plane order substantially unaltered



No expansion of interlayer distance

HSAG

HSAG-SP-M

HSAG-SP-T

HSAG-SP-T

HSAG-SP-M

HSAG

HSAG

HSAG-SP-M

HSAG-SP-T

D

_G

HSAG

HSAG-SP-M

HSAG-SP-T

Results from elemental, TGA, IR, XPS, Raman, XRD, HRTEM analysis

Few layers graphene

HSAG / PyC adducts

H

₂

N

OH

O

Si

O

O

O

NH

73

87

98

82

78

Functionalization Yield %

V. Barbera, A. Bernardi, A.Palazzolo, A. Rosengart, L. Brambilla, M. Galimberti Pure and Applied Chemistry 2018, 90(2), 253–270

Investigation with a model compound

N

CH

H

C

H

C

1,2,5-Trimethylpyrrole

(TMP)

Δ, Air

_{Δ, Air}

HSAG

Mechanism of the functionalization reaction

 Analysis of: liquids, HSAG/TMP adducts

 FT-IR and

1

_{H-NMR spectroscopies}

 FT-IR spectra generation with

Density Functional Theory (DFT)

quantum chemical modelling

TMP + Air - From 25°C to 150°C

25°C

150°C

130°C

80°C

A

bs

or

ban

c

e

(

a.

u.

)

800

1000

1200

1400

1600

1800

2000

Wavenumbers (cm

₎

out of plane

C-H bending

C=C stretching cyclic alkene

Inc

reas

ing tem

per

atur

e

N

CH

H

C

H

C

H

H

Δ, Air

N

CH

H

C

H

C

N

CH

H

C

H

C

TMP + HSAG - from 100°C to 150°C

Δ, Air

N

CH

H

C

H

C

Oxidation products

N

CH

H

C

H

C

H

H

800

1000

1200

1400

1600

1800

2000

A

bs

or

banc

e (

a.

u.

)

Wavenumbers (cm

₎

800

1000

1200

1400

1600

1800

2000

A

bs

or

banc

e (

a.

u.

)

out of plane

C-H bending

C=C stretching cyclic alkene

Inc

reas

ing tem

per

atur

e

25°C

80°C

130°C

100°C

150°C

Oxidation

HSAG

TMP oxidation product

1,5-dimethyl-1H-pyrrole-2-carbaldehyde

* Structure confirmed by means of NMR spectroscopy

FT-IR and 1_{H-NMR spectroscopies; FT-IR spectra generation with Density Functional Theory (DFT) quantum chemical modelling}

3

1

₂

Paal – Knorr Reaction

Carbocatalyzed Oxidation

Diels-Alder reaction

Carbon

allotrope

Facile functionalization of carbon materials

Hypothesis for the mechanism

O

O

H₂N R

+

FT-IR and 1_{H-NMR spectroscopies; FT-IR spectra generation with Density Functional Theory (DFT) quantum chemical modelling}

N H C R O O O R H₂N N CH3 H3C R N C H H₃C R O

Thanks to the carbon allotrope!

 Support:

absorption of pyrrole ring thanks to

π-π interaction



Oxidation

catalyst

: protection of pyrrole ring and oxidation of lateraI substituent

 Substrate

for the cycloaddition reaction, i.e. for functionalization

V. Barbera, L. Brambilla, M. Milani, A. Palazzolo, C. Castiglioni, A. Vitale, R. Bongiovanni, and M. Galimberti, 2019. Nanomaterials, 9(1), p.44. N H C R O O O R H2N N CH3 H₃C R N C H H₃C R O

Experimental determination

Theoretical predictions

Stable suspensions

in solvents

with different

δ

Computational model:

Hansen solubility parameters

CA / PyC adducts - Tuning of solubility parameters

V. Barbera, A. Bernardi, A.Palazzolo, A. Rosengart, L. Brambilla, M. Galimberti Pure and Applied Chemistry 2018, 90(2), 253–270

N

R

Evaluation of solubility parameters of HSAG-PyC - Hansen sphere

V. Barbera, A. Bernardi, A.Palazzolo, A. Rosengart, L. Brambilla, M. Galimberti Pure and Applied Chemistry 2018, 90(2), 253–270

HSAG-TMP

HSAG-DDcP

HSAG-APTESP

(

_*

)

_{Amount of SP on CA: 10 mass%}

Evaluation of solubility parameters of CA-SP - Radius comparison

0

2

4

6

8

10

12

14

Radius [MPa

½

_]

CB N234

CB - SP

CNT

CNT - SP

HSAG

HSAG - SP

Conc (g/L): 10 g/L, 30 g/L 200 g/L.

Large scale preparation

Inks and varnishes

Aerogels

Polyol dispersions

Polyurethanes

Carbon paper

Concrete with high

flexural strength

Rubber

nanocomposites

Conclusions

Andrea Bernardi Lucia Rubino Daniele Locatelli Fatima Margani

M.Sc. students

Simone Raciti,

Edoardo Testa

Roberto Guadagnin

Enrico Valentini

Luca Toscano

Nikola Pavlovich

Kasra Jahany

I

nnovative

S

ustainable

M

aterials Group

ISM

aterials

Silvia Guerra Sara Musto

Prof. Maurizio Galimberti

(Full Professor) Dr. Vincenzina Barbera (Assistant professor) Gea Prioglio

Postdocs

PhD students

instagram: @ismaterials.polimi

Thanks

for your attention!!